All-solid secondary battery and method of manufacturing the same

Patent metadata

Field	Value
Publication number	US-11424512-B2
Application number	US-201916580313-A
Country	US
Kind code	B2
Filing date	Sep 24, 2019
Priority date	Nov 2, 2018
Publication date	Aug 23, 2022
Grant date	Aug 23, 2022

Abstract

An all-solid secondary battery includes an anode layer; a cathode layer; a solid electrolyte layer interposed between the anode layer and the cathode layer, and including a first solid electrolyte; and a first bonding layer disposed between the cathode layer and the solid electrolyte layer, and comprising a second solid electrolyte, wherein the anode layer includes an anode current collector and an anode active material layer disposed on the anode current collector, and the anode active material layer includes a binder and an anode active material, wherein the cathode layer includes a cathode current collector and a cathode active material layer disposed on the cathode current collector, and wherein the second solid electrolyte has a Young's modulus which is less than a Young's modulus of the first solid electrolyte.

First claim

What is claimed is:

1. An all-solid secondary battery comprising:
an anode layer;
a cathode layer;
a solid electrolyte layer interposed between the anode layer and the cathode layer, the solid electrolyte layer comprising a first solid electrolyte; and
a first bonding layer disposed between the cathode layer and the solid electrolyte layer, the first bonding layer comprising a second solid electrolyte, wherein the first solid electrolyte and the second solid electrolyte have a different composition, and wherein a Young's modulus of the first solid electrolyte is about 5 gigapascals to about 10 gigapascals greater than a Young's modulus of the second solid electrolyte,
wherein the anode layer comprises
an anode current collector and an anode active material layer disposed on the anode current collector, and
the anode active material layer comprises a binder and an anode active material,

wherein the cathode layer comprises
a cathode current collector, and
a cathode active material layer disposed on the cathode current collector.

2. The all-solid secondary battery of claim 1 , wherein the anode active material does not contain an alkali metal.

3. The all-solid secondary battery of claim 1 , wherein the first bonding layer is interposed between the cathode active material layer and the solid electrolyte layer.

4. The all-solid secondary battery of claim 1 , wherein the first bonding layer is in contact with a surface of the cathode active material layer.

5. The all-solid secondary battery of claim 1 , wherein the first bonding layer comprises a sulfide solid electrolyte represented by Formula 1:
Li a M b PS c A d   Formula 1

wherein, in Formula 1,
0<a≤6, 0≤b≤6, 0<c<6, and 0≤d≤6;
M is Ge, Sn, or Si; and
A is one or more halogen elements.

6. The all-solid secondary battery of claim 1 , wherein the second solid electrolyte of the first bonding layer is an amorphous solid electrolyte, or a crystalline solid electrolyte, or a combination thereof.

7. The all-solid secondary battery of claim 1 , wherein the second solid electrolyte comprises a particle having a D50 particle diameter of 3 micrometers or less.

8. The all-solid secondary battery of claim 1 , wherein the first bonding layer has a thickness of 30 micrometers or less.

9. The all-solid secondary battery of claim 1 , wherein the first solid electrolyte comprises Li 2 S—P 2 S 5 , Li 2 S—P 2 S 5 —LiX wherein X is a halogen atom, Li 2 S—P 2 S 5 —Li 2 O, Li 2 S—P 2 S 5 —Li 2 O—LiI, Li 2 S—SiS 2 , Li 2 S—SiS 2 —LiI, Li 2 S—SiS 2 —LiBr, Li 2 S—SiS 2 —LiCl, Li 2 S—SiS 2 —B 2 S 3 —LiI, Li 2 S—SiS 2 —P 2 S 5 —LiI, Li 2 S—B 2 S 3 , Li 2 S—P 2 S 5 —Z m S n wherein m and n are positive numbers and Z is Ge, Zn, or Ga, Li 2 S—GeS 2 , Li 2 S—SiS 2 —Li 3 PO 4 , Li 2 S—SiS 2 —Li p MO q wherein p and q are independently from 1 to 4 and M is P, Si, Ge, B, Al, Ga, or In, Li x M′ y PS z A w wherein x, y, z, and w are independently from 0 to 6, M′ is Ge, Sn, or Si, and A is F, Cl, Br, or I; or
a combination thereof.

10. The all-solid secondary battery of claim 1 , wherein the first solid electrolyte comprises a particle having a D50 particle diameter of about 1 micrometer to about 3.5 micrometers.

11. The all-solid secondary battery of claim 1 , wherein the solid electrolyte layer has a thickness of about 10 micrometers to about 150 micrometers.

12. The all-solid secondary battery of claim 1 , wherein a second bonding layer is in contact with a surface of the solid electrolyte layer facing the anode active material layer, and
the second bonding layer comprises a third solid electrolyte having a Young's modulus which is less than a Young's modulus of the first solid electrolyte wherein the first solid electrolyte and the third solid electrolyte have a different composition.

13. The all-solid secondary battery of claim 12 , wherein the second bonding layer comprises an amorphous sulfide solid electrolyte.

14. The all-solid secondary battery of claim 1 , wherein the anode active material comprises amorphous carbon, gold, platinum, palladium, silicon, silver, aluminum, bismuth, tin, zinc, or a combination thereof.

15. The all-solid secondary battery of claim 1 , wherein the anode active material comprises amorphous carbon and gold, platinum, palladium, silicon, silver, aluminum, bismuth, tin, zinc, or a combination thereof.

16. The all-solid secondary battery of claim 1 , wherein the anode active material comprises a particle having a D50 particle diameter of 4 micrometers or less.

17. The all-solid secondary battery of claim 1 , wherein the anode active material layer has a thickness of about 1 micrometer to about 20 micrometers.

18. The all-solid secondary battery of claim 1 , further comprising an alkali metal deposit layer between the anode current collector and the anode active material layer during charge of the all-solid secondary battery.

19. The all-solid secondary battery of claim 1 , further comprising a film disposed between the anode current collector and the anode active material layer, and comprising a material disposed on the anode current collector which is capable of forming an alloy or compound with an alkali metal.

20. The all-solid secondary battery of claim 19 , wherein the material capable of forming an alloy with the alkali metal comprises silicon, magnesium, aluminum, lead, silver, tin, or a combination thereof.

21. The all-solid secondary battery of claim 19 , wherein the material capable of forming a compound with the alkali metal comprises carbon, titanium sulfide, iron sulfide, or a combination thereof.

22. The all-solid secondary battery of claim 19 , wherein the film has a thickness of about 1 nanometer to about 500 nanometers.

23. The all-solid secondary battery of claim 19 , further comprising an alkali metal deposit layer in an area on the anode active material layer, an area between the anode active material layer and the anode current collector, or a combination thereof.

24. The all-solid secondary battery of claim 1 , wherein the anode active material comprises amorphous carbon and silver, and
an alkali metal is precipitated in the anode active material to form an alloy with silver during charging of the all-solid secondary battery.

25. A method of manufacturing the all-solid secondary battery according to claim 1 , the method comprising:
providing a cathode layer;
compressing the cathode layer to form a compressed cathode layer;
providing an anode layer;
providing a solid electrolyte layer;
disposing the anode layer on the solid electrolyte layer to form a stack;
compressing the stack to form a compressed anode-electrolyte layer;
interposing a first bonding layer between the compressed cathode layer and the compressed anode-electrolyte layer; and
compressing the compressed cathode layer, the first bonding layer, and the compressed anode-electrolyte layer to form the all-solid secondary battery,
wherein the solid electrolyte layer comprises a first solid electrolyte, the first bonding layer comprises a second solid electrolyte, the first solid electrolyte and the second solid electrolyte have a different composition, and wherein a Young's modulus of the first solid electrolyte is about 5 gigapascals to about 10 gigapascals greater than a Young's modulus of the second solid electrolyte.

26. The method of claim 25 , wherein the compressing of the cathode layer, the compressing of the stack, and t

Assignees

• Samsung Electronics Co Ltd
• Samsung Sdi Co Ltd

Inventors

• Ku Junhwan
• Kang Hyorang

Classifications

• H01M2004/021

  Physical characteristics, e.g. porosity, surface area · CPC title

• H01M50/461 Primary

  with adhesive layers between electrodes and separators · CPC title

• H01M2004/027

  Negative electrodes · CPC title

• H01M10/0585 Primary

  of accumulators having only flat construction elements, i.e. flat positive electrodes, flat negative electrodes and flat separators · CPC title

• H01M4/38

  of elements or alloys · CPC title